CN102015784A - Polyethylene, process and catalyst composition for the preparation thereof - Google Patents
Polyethylene, process and catalyst composition for the preparation thereof Download PDFInfo
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- CN102015784A CN102015784A CN2008800230059A CN200880023005A CN102015784A CN 102015784 A CN102015784 A CN 102015784A CN 2008800230059 A CN2008800230059 A CN 2008800230059A CN 200880023005 A CN200880023005 A CN 200880023005A CN 102015784 A CN102015784 A CN 102015784A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
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Abstract
A multimodal polyethylene having an inverse comonomer distribution, as well as a process carried out in a single reactor in the presence of a mixed catalyst composition comprising two different polymerization catalysts, are described. The multimodal polyethylene has a density of 0 915 - 0 970 g/cm<3>, a weight average molar mass Mw of 100 000 - 900 000 g/mol, and a polydispersity Mw/Mn of at least 15. The at least one homopolymer has a density of 0 950 - 0 975 g/cm<3>, a weight average molar mass Mw of 10 000 - 90 000 g/mol and a polydispersity Mw/Mn higher than 3 and lower than 10, and the at least one copolymer has a polydispersity Mw/Mn between 8 and 80.
Description
Invention field
The present invention relates to polyethylene and be applicable to method and the catalyst composition for preparing it.
Multimodal polyethylene is known, and its performance mainly depends on the character and the poly method of preparation of the ethene polymers fraction of making them, and especially depends on the technology type that is used for making it.Implement in the different step of manufacturing process being used for, what play a crucial role is for from monomer, promptly, obtain polyethylene and implement selected catalyst system in (being total to) polymerization procedure (multistep) from ethene and randomly a kind of other comonomer or multiple other comonomer.
In this specification sheets and claim subsequently, except as otherwise noted, otherwise term " polymer " " be used to refer to homopolymer; promptly comprise derived from the unitary polymkeric substance of the monomeric repeated monomer of kind; and multipolymer, promptly comprise derived from least 2 kinds of unitary polymkeric substance of the monomeric repeated monomer of inhomogeneity, under one situation of back; will be called copolymer, terpolymer etc., and depend on the kind number of existing different monomers.
Similarly, except as otherwise noted, in this specification sheets and claim subsequently, term " polyethylene " is used to refer to the multipolymer of Alathon and ethene and another kind of at least comonomer.
Similarly, except as otherwise noted, term " polymerization " is used to refer to homopolymerization, promptly derived from the unitary polymerization of similar monomeric repeated monomer, and copolymerization, i.e. at least 2 kinds of monomeric polymerizations of inhomogeneity.
In this specification sheets and claim subsequently, term " Alathon " is used to refer to and comprises the repetition ethylene monomer unit, the polymkeric substance that has the inhomogeneity comonomer that exists with finite quantity, under any circumstance, make the melting temperature (Tm) Tm of polymkeric substance be equal to or higher than 125 ℃, wherein melting temperature (Tm) Tm is the temperature of melting peak highest point, as hereinafter describing better.Tm presses ISO11357-3 and measures: the temperature rise rate with 20 ℃/min heats earlier, reach 200 ℃ until temperature,, reach-10 ℃ until temperature with the rate of cooling dynamic crystallization of 20 ℃/min, temperature rise rate with 20 ℃/min heats for the second time again, reaches 200 ℃ until temperature.Melting temperature (Tm) Tm (adding the maximum of pining for melting peak for the second time) adds to pine for heat content reaches maximum to the curve of temperature temperature for the second time.
In this specification sheets and claim subsequently, term " multipolymer of ethene " is used to refer to the polymkeric substance that comprises repetition ethylene monomer unit and at least a other inhomogeneity comonomer, described at least a inhomogeneity comonomer exists with the amount greater than preset value, under any circumstance, make the melting temperature (Tm) Tm of polymkeric substance be lower than 125 ℃.
Multimodal polyethylene has the melt flow-disturbing that reduces and more preferred than unimodal polyethylene, because the application of blowing with predetermined physical strength and/or film and so on is had better properties.The molecular mass distribution curve of multimodal polyethylene generally has a more than molecular mass peak, because there is the visibly different polymer fractions of multiple molecular mass.Unimodal polyethylene has unimodal molecular mass distribution curve, and the curve at single peak is promptly arranged, because there is the single polymer fractions with given molecular mass.The molecular mass of broad distributes and can help making multimodal polyethylene than the easier processing of unimodal poly-Class B.
Prior art
The various different methods of producing multimodal polyethylene are known, comprise post-reactor or melt blended, use staged reactor, and by using catalyzer catalysis in single reactor that can generate this multimodal polyethylene.The poly performance of method affect because the performance of multimodal polyethylene not only depends on the performance of its single polymer fractions, and depends on the mixing quality of these fractions.Bad mixing quality especially causes the goods stress crack resistant made by this quasi-polyethylene low, and impairs creep behaviour.
As for the melt blended technology in forcing machine, that is expensive, complicated and technology consuming time.
In technology based on staged reactor, generally have the reactor of two series operations at least, each reactor all moves under visibly different hydrogen concentration, to obtain visibly different each polyethylene fraction of molecular weight.
In this specification sheets and claim subsequently, term " molecular weight " is used to refer to weight-average molar mass M
w, except as otherwise noted.
For example, about the technology of in the reactor of two arranged in series, carrying out, the shortcoming of this technology except the complicacy and cost that cause because will carry out, is that also having to add relatively large hydrogen could generate the fraction with lower molecular weight in two reactors.Therefore, contents of ethylene is low in the polyethylene that in this way obtains, and especially in low molecular weight fraction, generally all is lower than 0.3.
In addition, for comonomer or the hydrogen (or any other molecular weight regulator) that prevents to be added in first reactor enters second reactor, technical very complicated.
Perhaps, also can make multimodal polyethylene with single reactor, method is to use the catalyst composition that comprises at least 2 kinds of different ethylene rolymerization catalysts, to generate visibly different separately polyethylene fraction.
The catalyst composition that use comprises at least 2 kinds of different ethylene rolymerization catalysts of Ziegler type or metallocene-type is known.So for example, the WO95/11264 instruction is produced each polyolefine with different weight-average molar masses with the combination of these 2 kinds of catalyzer, generates the polyethylene with wide molecular mass distribution thus.
About this point, know, use formed ethene of classical Ziegler-Natta catalyst and more senior 1-alkene based on titanium, multipolymer as propylene, 1-butylene, 1-amylene, 1-hexene or 1-octene, be called LLDPE (LLDPE), be different from the LLDPE that makes with metallocene.Because of sneaking into side chain number that comonomer forms and their distribution, be called SCBD (short-chain branched distribution), depend on the character of catalyzer especially consumingly.The number of side chain and distribution transfer to influence the crystallization behavior of ethylene copolymer again, and therefore influence its mechanical property.Though the flowing property of these ethylene copolymers and therefore the processibility molecular mass and the molecular mass that mainly depend on them distribute, but in the particular process method, as in film is extruded, therein the crystallization behavior of film extrudate cooling period ethylene copolymer be the decision film can extrude how soon with film quality important factor how, short-chain branched distribution is also worked.
The polyethylene made from the transition metal complex that comprises other part outside the cyclopentadienyl ligands also is known.For example, WO 04/074333 has described as 2 of the yttrium of the catalyzer of polymerization conjugated dienes, lanthanon or acitinide metal, 6-two [1-(2,6-di-isopropyl phenylimino) ethyl] pyridine complex.WO 98/27124 discloses as 2 of the iron of the catalyzer of equal polymerization or copolymerization of ethylene and cobalt, 6-two (imino-) pyridyl complex compound.WO 99/46302 discloses the catalyst composition that is used for alpha-olefine polymerizing, and it comprises (a) 2,6-two (imino-) pyridine iron component and (b) another kind of catalyzer, i.e. zirconocene or Ziegler catalyst.J.Am.Chem.Soc.2005,127,13019～13029 have described the preparation and they comparisons to ethylene polymerization of several diimino pyridyl iron catalysts.WO 05/103096 has described and has comprised (a) 2,6-two (imino-) pyridine iron component and (b) another kind of catalyzer, the i.e. catalyst composition of hafnocene catalyzer.
Summary of the invention
The purpose of this invention is to provide, especially but non-special project, in working method, in extruding as film, have the multimodal polyethylene of predetermined mechanical property and processibility concurrently.
Another object of the present invention provides has the predetermined active catalyzer that is suitable for preparing above-mentioned multimodal polyethylene.
Another purpose of the present invention provides the preparation method of above-mentioned multimodal polyethylene.
Above-mentioned purpose is by providing the multimodal polyethylene with reverse comonomer distribution to be achieved, this method advantageously allows to obtain improved mechanical property and at least a first ethene polymers fraction and at least a second ethene polymers fraction preset value of polymolecularity separately, and this advantageously allows to obtain improved processibility.More very it, the applicant has been found that, have lower molecular weight and comprise that the described at least a first ethene polymers fraction of Alathon should have narrower molecular mass distribution, and have higher molecular weight and comprise that the described at least a second ethene polymers fraction of ethylene copolymer should have the molecular mass distribution of broad.
Oppositely comonomer distribution is following a kind of comonomer distribution: comonomer only adds with the ethene polymers fraction of higher molecular weight basically therein, the comonomer distribution that is referred to as to have with lower molecular weight fraction wherein higher comonomer content in the field is opposite, vice versa, as can by to each ethene polymers fraction with traditional non-single-point catalyst, as Ziegler-Natta catalyst, can obtain, and contain useful single-point catalyst, as metallocene catalyst, the multimodal ethylene polymkeric substance of all ethene polymers fractions of generation has basic comonomer distribution uniformly.
The invention provides and comprise at least a first ethene polymers fraction that comprises the Alathon with first molecular weight and at least one comprises the multimodal polyethylene of the second ethene polymers fraction of the ethylene copolymer with second molecular weight that is higher than described first molecular weight, the density of this multimodal polyethylene is 0.915～0.970g/cm
3, weight-average molar mass M
wBe 100 000～900 000g/mol and polymolecularity M
w/ M
nBe at least 15, wherein, the density of at least a homopolymer is 0.950～0.975g/cm
3, weight-average molar mass M
wBe 10 000～90 000g/mol and polymolecularity M
w/ M
nGreater than 3 and less than 10, and the polymolecularity M of at least a multipolymer wherein
w/ M
nBe 8～80.
The density of multimodal polyethylene is preferably 0.920～0.960g/cm
3, more preferably 0.940～0.955g/cm
3According to another preferred embodiment of the present invention, the density of multimodal polyethylene is 0.930～0.967g/cm
3
The weight-average molar mass M of multimodal polyethylene
wBe preferably 150 000～800 000g/mol, more preferably 200 000～750 000g/mol.
Preferred multimodal polyethylene has polymolecularity, i.e. weight-average molar mass M
wWith mumber average molar mass M
nRatio be 15～180, more preferably 15～150, more preferably 20～150, and again more preferably 20～130.
The density of preferred multimodal polyethylene homopolymer is 0.955～0.975g/cm
3, more preferably 0.960～0.970g/cm
3
The weight-average molar mass M of preferred multimodal polyethylene homopolymer
wBe 20 000～80 000g/mol, more preferably 30 000～70 000g/mol.
The polymolecularity of multimodal polyethylene homopolymer is 3＜M
w/ M
n＜10, preferred 3＜M
w/ M
n＜8, preferred 4＜M
w/ M
n＜8, more preferably 4＜M
w/ M
n＜7,4.5＜M especially
w/ M
n＜7.
Preferably, the density of multimodal polyethylene multipolymer is 0.910～0.965g/cm
3, preferred 0.920～0.960g/cm
3, more preferably 0.939～0.955g/cm
3
Preferably, the weight-average molar mass M of multimodal polyethylene multipolymer
wBe 150 000～2 000000g/mol, preferred 180 000～1 000 000g/mol, more preferably 200 000～800 000g/mol.
The polymolecularity of preferred multimodal polyethylene multipolymer is 8～80, more preferably 10～50, and again more preferably 12～30.
According to the preferred embodiments of the invention, multimodal polyethylene contains at least 1.5 CH
3Base/1000 carbon atoms, preferred 1.5～15 CH
3Base/1000 carbon atoms, more preferably 2.5～10 CH again
3Base/1000 carbon atoms.
In this specification sheets and claim subsequently, CH
3Radix/1000 carbon atom is used
13C-NMR, as James.C.Randall, JMS-REV, Macromol.Chem.Phys., C29 (2﹠amp; 3), described such mensuration of 201-317 (1989), and be referred to as CH
3Base total content/1000 carbon atoms.
Preferred multimodal polyethylene contains at least 0.3 vinyl/1000 carbon atom, preferred at least 0.5 vinyl/1000 carbon atom, preferred 0.5～3 vinyl/1000 carbon atom, preferred 0.5～2 vinyl/1000 carbon atom, preferred 0.5～1.5 vinyl/1000 carbon atom.According to another preferred embodiment, multimodal polyethylene preferably contains and is less than 5 vinyl/1000 carbon atoms, preferred 1～3 vinyl/1000 carbon atom, preferred 2～3 vinyl/1000 carbon atoms.
The preferred described at least a first ethene polymers fraction contains at least 0.3 vinyl/1000 carbon atom, preferred at least 0.5 vinyl/1000 carbon atom, preferred 0.5～5 vinyl/1000 carbon atom, preferred 0.5～3 vinyl/1000 carbon atom, preferred 0.5～2 vinyl/1000 carbon atom, preferred 0.5～1.5 vinyl/1000 carbon atom.According to another preferred embodiment, the described at least a first ethene polymers fraction preferably contains and is less than 5 vinyl/1000 carbon atoms, preferred 1～3 vinyl/1000 carbon atom, preferred 2～3 vinyl/1000 carbon atoms.
In this specification sheets and claim subsequently, contents of ethylene/1000 carbon atom is meant-CH=CH
2The content of group, and use IR, ASTM D 6248-98 measures.
Preferred multimodal polyethylene contains at least 0.1 vinylidene/1000 carbon atom, more preferably 0.1～0.5 vinylidene/1000 carbon atom, more preferably 0.1～0.25 vinylidene/1000 carbon atom again.
In this specification sheets and claim subsequently, vinylidene content/1000 a carbon atom IR, ASTM D 6248-98 measures.
Usually the polymkeric substance termination reaction after ethene being embedded is owing to vinyl, and inferior ethene end group forms after the polymkeric substance termination reaction after comonomer embeds usually.
Depend on the application of multimodal polyethylene, perhaps preferably make vinylidene and vinyl functionalized subsequently or crosslinked, vinyl is more suitable for usually in this class subsequent reactions.
Therefore, multimodal polyethylene of the present invention need in the follow-up functionalized or crosslinked application, as pipeline or tackiness agent to be specially adapted to.
Ethylene copolymer in the multimodal polyethylene preferably comprises at least a alpha-olefin as comonomer.Preferred alpha-olefin is all alpha-olefins that contain 3～12 carbon atoms, as propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene.The ethylene copolymer of multimodal polyethylene preferably comprises at least a 1-alkene that contains 4～8 carbon atoms, as 1-butylene, 1-amylene, 1-hexene, 4-methylpentene or 1-octene.Be preferably selected from least a alpha-olefin of 1-butylene, 1-hexene and 1-octene especially.
Multimodal polyethylene of the present invention can be used, and for example, is comprising the technology of carrying out in the presence of the mixed catalyst composition of 2 kinds of various polymerization catalysts and obtain in single reactor, and is as mentioned below.
Therefore, the invention provides the catalyst composition that is specially adapted to make above-mentioned multimodal polyethylene.
It is at least a based on the chrome catalysts of chromic oxide and (B) iron catalyst of at least a formula (I) that catalyst composition of the present invention comprises (A),
Wherein each symbol has at suitable local integrated structure (II) and (I) or the following meaning that only structure (I) is further provided here:
F and G are independently from each other following one group:
R
A, R
BRepresent hydrogen, C independently of one another
1～C
20-alkyl, C
2～C
20-thiazolinyl, C
6～C
20Have the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl, or SiR
11A 3, organic group R wherein
A, R
BAlso can be replaced by halogen, and/or in all cases, two radicals R
A, R
BAlso can be bonded to 5-or 6-unit ring each other,
R
C, R
DRepresent hydrogen, C independently of one another
1～C
20-alkyl, C
2～C
20-thiazolinyl, C
6～C
20Have the aralkyl or the SiR that have 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl
11A 3, organic group R wherein
C, R
DAlso can be replaced by halogen, and/or in all cases, two radicals R
C, R
DAlso can be bonded to 5-or 6-unit ring each other,
R
11ARepresent hydrogen, C independently of one another
1～C
22-alkyl, C
2～C
22-thiazolinyl, C
6～C
22Have the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl, and/or two radicals R
11AAlso can be bonded to 5-or 6-unit ring each other,
According to a preferred embodiment, described at least a iron catalyst has formula (II):
Wherein each symbol has following meaning:
R
1-R
2Represent hydrogen, C independently of one another
1～C
22-alkyl, C
2～C
22-thiazolinyl, C
6～C
22Have in-aryl, the alkyl and have the aralkyl of 6～20 carbon atoms in 1～10 carbon atom and the aryl or comprise at least one 5-, 6-or 7-unit heterocyclic radical, wherein organic group R from the atom of N, P, O or S
1-R
2Also can be by halogen, NR
16 2, OR
16Or SiR
17 3Replace and/or two radicals R
1-R
2Also can with R
3-R
5Be bonded to 5-, 6-or 7-unit ring,
R
3-R
15Represent hydrogen, C independently of one another
1～C
22-alkyl, C
2～C
22-thiazolinyl, C
6～C
22Have the aralkyl, the NR that have 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl
16 2, OR
16, halogen, SiR
17 3Or comprise at least one 5-, 6-or 7-unit heterocyclic radical, wherein organic group R from the atom of N, P, O or S
3-R
15Also can be by halogen, NR
16 2, OR
16Or SiR
17 3Replace and/or two radicals R in all cases
3-R
5Bonding and/or two radicals R each other in all cases
6-R
10Also can be bonded to 5-, 6-or 7-unit ring each other, and/or under any circumstance, two radicals R
11-R
15Also can be bonded to 5-, 6-or 7-unit ring each other, and/or under any circumstance, two radicals R
3-R
5Bonding and/or under any circumstance two radicals R each other
6-R
10Be bonded to 5-, 6-or 7-unit heterocyclic radical each other, and/or two radicals R under any circumstance
11-R
15Be bonded to 5-, 6-or 7-unit heterocyclic radical each other, described heterocyclic radical comprises at least one atom from N, P, O or S, wherein radicals R
6-R
15In be chlorine, bromine, iodine, CF one of at least
3Or OR
11,
R wherein
6-R
8And R
11-R
13In at least one R base be chlorine, bromine, iodine, CF
3Or OR
11,
R
16Represent hydrogen, C independently of one another
1～C
22-alkyl, C
2～C
22-thiazolinyl, C
6～C
22Have the aralkyl or the SiR that have 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl
17 3, organic group R wherein
16Also can be replaced by halogen, and in all cases, two radicals R
16Also can be bonded to 5-or 6-unit ring,
R
17Represent hydrogen, C independently of one another
1～C
22-alkyl, C
2～C
22-thiazolinyl, C
6～C
22-aryl perhaps has the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in the alkyl, and in all cases, two radicals R
17Also can be bonded to 5-or 6-unit ring,
E
1-E
3Represent carbon, nitrogen or phosphorus independently of one another, especially carbon and
UE
1-E
3When being nitrogen or phosphorus, be 0 independently of one another, E
1-E
3When being carbon, be 1,
X represents fluorine, chlorine, bromine, iodine, hydrogen, C independently of one another
1～C
10-alkyl, C
2～C
10-thiazolinyl, C
6～C
20Have the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl, wherein X also can be by R round and round for organic radical
18, NR
18 2, OR
18, SR
18, SO
3R
18, OC (O) R
18, CN, SCN, beta-diketon acid group, CO, BF
4 -, PF
6 -Or non-coordination macroanion replaces, and radicals X wherein, if randomly/suitable, and bonding each other,
R
18Represent hydrogen, C independently of one another
1～C
20-alkyl, C
2～C
20-thiazolinyl, C
6～C
20Have the aralkyl or the SiR that have 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl
19 3, organic radical R round and round wherein
18Also can be by halogen or nitrogenous-and contain oxygen-Ji and replace, and in all cases, two radicals R
18Also can be bonded to 5-or 6-unit ring,
R
19Represent hydrogen, C independently of one another
1～C
20-alkyl, C
2～C
20-thiazolinyl, C
6～C
20Has the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl or the alkyl, wherein organic radical R round and round
19Also can be by halogen or nitrogenous-and contain oxygen-Ji and replace, and in all cases, two radicals R
19Also can be bonded to 5-or 6-unit ring,
S is 1,2,3 or 4, especially 2 or 3,
D be neutral give body and
T is 0～4, especially 0,1 or 2.
Therefore the present invention provides also that to comprise (A) at least a based on the chrome catalysts of chromic oxide and (B) catalyst composition of the iron catalyst of at least a formula (II).
3 atom E of intramolecularly
1-E
3Can be the same or different.If E
1Be phosphorus, E then
2-E
3Preferably respectively be carbon.If E
1Be nitrogen, E then
2And E
3Preferably respectively be nitrogen or carbon, especially carbon.
U is at E
1-E
3When being nitrogen or phosphorus, be 0 independently of one another, at E
1-E
3When being carbon, be 1.
R
1-R
2Can in broad scope, change.Possible carbon organic substituent R
1-R
2As follows: C
1～C
22-alkyl can be line style or branching, for example, and methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl; 5-～7-unit cycloalkyl, it can be with C again
1～C
10-alkyl and/or C
6～C
10-aryl is a substituting group, for example, and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl; C
2～C
22-thiazolinyl, can be line style, ring-type or branching, and therein, two keys can be internal double bond or terminal double bond, for example, vinyl, 1-allyl group, 2-allyl group, 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base; C
6～C
22-aryl can be replaced by other alkyl, for example, phenyl, naphthyl, xenyl, anthryl, adjacent-,-or right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2,6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl; Or aralkyl, can be replaced by other alkyl, for example, benzyl, adjacent-,-or right-methyl-benzyl, 1-or 2-ethylphenyl, wherein, two radicals R
1-R
2Also can be combined into 5-, 6-or 7-unit ring, and/or two R of adjacent group group
1-R
2Also can be combined into and contain at least one 5-, 6-or 7-unit heterocycle from the atom of N, P, O and S, and/or organic group R
1-R
2Can also be replaced as fluorine, chlorine or bromine by halogen.In addition, R
3-R
15Also can be amino N R
16 2Or SiR
17 3, alkoxyl group or aryloxy OR
16, for example, dimethylamino, N-pyrrolidyl, pieolinyl, methoxyl group, oxyethyl group or isopropoxy or halogen are as fluorine, chlorine or bromine.The radicals R that other is possible
16And R
17Discuss more fully hereinafter.Two R
16And/or R
17Also can be combined into 5-or 6-unit ring.SiR
17 3Base also can pass through oxygen or nitrogen and E
1-E
3Bonding.R
17Example be trimethylsiloxy, silicoheptane alcoxyl base, butyl dimethylsilane oxygen base, tributyl siloxy-or three-tertiary butyl siloxy-.
Substituent R
3-R
15Can in broad scope, change, as long as R
6-R
15In at least one radicals R be chlorine, bromine and iodine, CF
3Or OR
11Get final product.Possible carbon organic substituent R
3-R
15As follows: C
1～C
22-alkyl can be line style or branching, for example, and methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl; 5-～7-unit cycloalkyl, it can be with C again
1～C
10-alkyl and/or C
6～C
10-aryl is a substituting group, for example, and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl; C
2～C
22-thiazolinyl, can be line style, ring-type or branching, and therein, two keys can be internal double bond or terminal double bond, for example, vinyl, 1-allyl group, 2-allyl group, 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base; C
6～C
22-aryl can be replaced by other alkyl, for example, phenyl, naphthyl, xenyl, anthryl, adjacent-,-or right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2,6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl; Or the aralkyl that can be replaced by other alkyl, for example, benzyl, adjacent-,-or right-methyl-benzyl, 1-or 2-ethylphenyl, wherein, two radicals R
3-R
5And/or two adjacent group R
6-R
15Also can be combined into 5-, 6-or 7-unit ring and/or R
3-R
5In two adjacent groups and/or R
6-R
15In two adjacent groups can be combined into 5-, 6-or 7-unit heterocycle, contain at least one atom in the described heterocycle, and/or organic group R from N, P, O and S
3-R
5And/or R
6-R
15Also can be by halogen, as fluorine, chlorine or bromine, replace.In addition, R
3-R
15Also can be amino N R
16 2Or SiR
17 3, alkoxyl group or aryloxy OR
16, as dimethylamino, N-pyrrolidyl, pieolinyl, methoxyl group, oxyethyl group or isopropoxy or halogen, as fluorine, chlorine or bromine.The radicals R that other is possible
16And R
17Discuss more fully hereinafter.Two R
16And/or R
17Also can be combined into 5-or 6-unit ring.SiR
17 3Base also can pass through oxygen or nitrogen and E
1-E
3Bonding.R
17Example be trimethylsiloxy, silicoheptane alcoxyl base, butyl dimethylsilane oxygen base, tributyl siloxy-or three-tertiary butyl siloxy-.
Preferred radicals R
3-R
5Be hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, neighbour-dialkyl group-or phenyl of replacing of two chloro-, trialkyl-or three chloro-phenyl, naphthyl, xenyl and anthryl of replacing.Particularly preferred organosilicon substituting group is the trialkylsilkl that has 1～10 carbon atom in the alkyl, especially trimethyl silyl.
Preferred radicals R
6-R
15Be hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, fluorine, chlorine and bromine, wherein radicals R
6-R
15In be chlorine, bromine, iodine, CF one of at least
3Or OR
11
Preferred R
6-R
8And R
11-R
13In at least one R base be chlorine, bromine or CF
3, and R
6-R
8And R
11-R
13In at least one R base be hydrogen or C
1～C
4-alkyl, wherein alkyl can be line style or branching, especially methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl.
Especially, R
6-R
8And R
11-R
13In at least one R base be chlorine or bromine, and R
6-R
8And R
11-R
13In at least one R base be hydrogen or methyl.
Preferred R
6And/or R
11Be chlorine or bromine and R
7, R
8, R
12And/or R
13Be hydrogen or methyl.In another preferred embodiment of the present invention, R
6And R
8, and/or R
11And R
13Be chlorine or bromine, and R
7And/or R
12Be hydrogen or methyl.In another preferred embodiment, R
6With R
11Identical, and/or R
7With R
12Identical, and/or R
8With R
13Identical, wherein at least one pair of all the other identical R is chlorine or bromines.In another preferred embodiment, R
6With R
11Difference, and/or R
7With R
12Difference, and/or R
8With R
13Difference, wherein remaining R is a chlorine or bromine at least.Preferred especially iron component, R therein
6-R
8And/or R
11-R
13In at least one all the other R be chlorine.
Especially, R
9, R
10, R
14And R
15In at least one radicals R be hydrogen or C
1～C
22-alkyl, described C
1～C
22-alkyl also can be replaced by halogen, for example, and methyl, trifluoromethyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or vinyl.Preferred especially R
9, R
10, R
14And R
15Be hydrogen or methyl, ethyl, n-propyl, normal-butyl, preferred hydrogen.Especially R
9, R
10, R
14And R
15All identical.
Change R
16Base can be regulated subtly, and for example, physicals is as solubleness.Possible carbon organic substituent R
16As follows: C
1～C
20-alkyl, can be line style or branching, for example, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, 5-～7-unit cycloalkyl, it can be with C again
6～C
20-aryl is a substituting group, for example, and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl; C
2～C
20-thiazolinyl, can be line style, ring-type or branching, and therein, two keys can be internal double bond or terminal double bond, for example, vinyl, 1-allyl group, 2-allyl group, 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base; C
6～C
20-aryl can and/or contain N-or contain the O-base and replaces by other alkyl, for example, phenyl, naphthyl, xenyl, anthryl, adjacent-,-or right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2,6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4, the 5-trimethylphenyl, 2-p-methoxy-phenyl, 2-N, N-dimethylaminophenyl; Or the aralkyl that can be replaced by other alkyl, for example, benzyl, adjacent-,-or right-methyl-benzyl, 1-or 2-ethylphenyl, wherein, two radicals R
16Can also be combined into 5-or 6-unit ring and organic group R
16Can also be by halogen, as fluorine, chlorine or bromine, replace.
Organosilicon substituting group SiR
17 3In possible R
17Basic and above to R
1-R
2Described identical, two R wherein
17Also can be combined into 5-or 6-unit ring, for example, trimethyl silyl, triethylsilyl, butyl dimetylsilyl, tributyl silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.Preferably use C
1～C
10-alkyl as methyl, ethyl, n-propyl, normal-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, also has vinyl, allyl group, benzyl and phenyl as R
17Base.
X ligand is derived from, and for example, to being used for the selection of suitable initial metallic compound of synthetic iron complex, but also can change subsequently.Possible X ligand is halogen especially, as fluorine, chlorine, bromine or iodine, especially chlorine.Alkyl also is the available X ligand as methyl, ethyl, propyl group, butyl, vinyl, allyl group, phenyl or benzyl, and wherein organic group X also can be by R
18Replace.As other X ligand, can mention, be specially to refer to trifluoro-acetate, BF anything but for example purely
- 4, PF
- 6With weak coordination or non-coordination anion (for example, with reference to S.Strauss, Chem.Rev.1993,93,927-942), for example, B (C
6F
5)
- 4Acid amides, alkoxide, sulfonate, carboxylate salt and beta-diketon hydrochlorate also are useful especially X ligand.They especially preferably replace X ligand, because can obtain from raw material cheap and that be easy to get with some these classes.Therefore particularly preferred embodiment is, X is dimethylformamide, methoxide, b-oxide, isopropoxide, phenates, naphthalene oxide compound, fluoroform sulphonate, right-the toluene iodate, acetate or acetylacetonate therein.
The quantity s of X ligand depends on the oxidation state of iron.Therefore quantity s cannot treat different things as the same.The oxidation state of iron is normally well known to those skilled in the art in the catalytic activity complex compound.But may not correspond to the complex compound of active catalyst oxidation state with its oxidation state yet.Can suitably reduce or this class complex compound of oxidation with the activator that is fit to then.Preferably with oxidation state be+3 or+2 iron complex.
The D right and wrong are charged gives body, especially non-charged Lewis base or Lewis acid, for example, amine, alcohols, ethers, ketone, aldehydes, ester class, sulfide-based or phosphine class, they can be bonded in the iron and exist as the residual solvent from the iron complex preparation in the heart or still.
The quantity t of part D can be 0～4, and often depends on solvent and the gained part exsiccant time for preparing iron complex therein, and also may be non-integer therefore, as 0.5 or 1.5.T especially 0,1～2.
Preferred complex compound (B) is 2,6-two [1-(2-chloro-4,6-3,5-dimethylphenyl imino-) ethyl] pyridine iron (II) muriate; 2,6-two [1-(2-chloro-6-aminomethyl phenyl imino-) ethyl] pyridine iron (II) dichloride; 2,6-two [1-(2,6-dichlorophenyl imino-) ethyl] pyridine iron (II) dichloride; 2,6-two [1-(2,4-two chloro-6-methyl-phenyliminos) ethyl] pyridine iron (II) dichloride; 2,6-two [1-(2,6-difluorophenyl imino-) ethyl] pyridine iron (II) dichloride; 2,6-two [1-(2,6-dibromo phenyl imino-) ethyl] pyridine iron (II) dichloride or dibromide separately or tribromide.
The preparation of iron complex (B) is described in, for example, J.Am.Chem.Soc.120, ff (1998) p.4049, J.Chem.Soc. is among Chem.Commun 1998,849 and the WO 98/27124.
Generally speaking, all can be used to prepare catalyzer (A) in the catalyst composition of the present invention based on all chrome catalysts of chromic oxide, as long as the ethylene copolymer that they have defined characteristics in the claims 1 with iron catalyst (B) generation.Generally speaking, this class chrome catalysts also is called philip catalyst and is that known (for example, their composition and preparation method are described in M.P.McDaniel in this area, Adv.Cat 33,7-98 (19B5), US 5,363, in 915, all these all draw in this for reference.Preferably use load chromic oxide or Phillips catalyzer.
Based on the chrome catalysts of chromic oxide is well known in the art and can be available from a plurality of manufacturers.As known, chrome catalysts is generally produced as follows: with chromium (catalyst precursor) doping inorganic carrier such as silica gel or aluminum oxide, preferably contain the chromium active ingredient from solution, or under the situation of volatile compound, from vapor phase.The chromium cpd that is suitable for is chromic oxide (VI), chromic salts, as chromium nitrate (III) and chromium acetate (III), coordination compound, as chromium acetylacetonate (III), or the organometallic compound of Chromium hexacarbonyl or chromium, as two (cyclopentadienyl) chromium (II), organic chromium ester or diaryl (aren?) chromium (0).Preferably use chromium nitrate (III).For obtaining polymerization-active catalyst, be under preset temperature, preferred 500～900 ℃, more preferably 550～650 ℃, in oxidizing atmosphere, preferably in air, the chrome catalysts precursor is mixed in thermal treatment.According to the preferred embodiment of the method for preparing chrome catalysts, can use reductive agent, as carbon monoxide or hydrogen, the oxide catalyst precursor is stood in advance-reduction step.Be somebody's turn to do pre--reduction step preferably at 300～400 ℃, more preferably carry out between 320～480 ℃, the preferably treatment cycle is 5min～48h, more preferably 1～10h.
The mol ratio of chrome catalysts (A) and iron catalyst (B) is generally 1: 100～and 100: 1, preferred 1: 10～10: 1, especially preferred 1: 5～5: 1.Also preferred (A) and preferred embodiment (B) in (A) and combination (B).
Catalyst composition of the present invention can use separately, also can use with other component as the catalyst system of olefinic polymerization.Therefore the present invention also provides and comprises, except that catalyzer (A) with (B), at least a organic or inorganic carrier (H), and/or at least a activating compounds (J), and/or the catalyst composition (K) of at least a metallic compound of metal in 1,2 or 13 families in the periodictable.
As possible solid support material, preferably use silica gel, magnesium chloride, aluminum oxide, mesoporous material, aluminosilicate, hydrotalcite and organic polymer, polymkeric substance as polyethylene, polypropylene, polystyrene, tetrafluoroethylene or band polar functional group, for example, the multipolymer of ethene and acrylate, propenal or vinyl-acetic ester.In a preferred embodiment of the invention, with supported chromium catalysts and supported ferric catalyst.In particularly preferred embodiments, chrome catalysts and iron catalyst are on identical general carrier, to guarantee the space proximity that the different catalysts center is nearer and therefore to guarantee that formed different mixed with polymers is good.
Preferably use carrier in small, broken bits (H), this carrier can be the inert solid of any organic or inorganic.Carrier (H) especially can be a porous support, as talcum, sheet silicate or inorganic oxide.Preferably
The carrier (H) that uses has 10～1000m
2/ g, preferred 200～400m
2The specific surface area of/g, and preferably have the pore volume of 0.1～5ml/g.The average particle size particle size of carrier in small, broken bits is generally 1～500 μ m, especially 30～70 μ m.
Being suitable for doing the inorganic oxide of carrier (H) can be in the 2nd, 3,4,5,13,14,15 and 16 families of the periodic table of elements seek in the oxide compound of element.Preferred elements calcium, aluminium, silicon, magnesium or titanyl compound or mixed oxide and corresponding oxide mixture; Randomly, also can use ZrO
2Or B
2O
3Preferred oxide compound is a silicon-dioxide, especially silica gel or pyrogenic silica form, or aluminum oxide.The example of particularly preferred carrier is spray-dired SiO
2, especially have 1.0～3.0ml/g, preferred 1.2～2.2ml/g, the more preferably pore volume of 1.4～1.9ml/g and 100～500m
2/ g, preferred 200～400m
2Those of/g surface-area (BET).This series products has commodity to purchase, for example, and the Silica XPO 2107 that Grace sells.
Inorganic carrier (H) can be heat-treated, for example, and in order to remove the water of absorption.This drying treatment is generally at 80～300 ℃, and preferred 100～200 ℃ are carried out, and is preferably reducing pressure and/or carrying out in inert gas such as nitrogen or argon gas stream.Inorganic carrier (H) also can be calcined, and in this case, by 200～1000 ℃ processing, regulates lip-deep OH base concentration and can change the solid structure.Also available siccative commonly used of carrier such as metal alkylide, preferred alkyl aluminium, chlorosilane or SiCl
4, or methylaluminoxane is carried out chemical treatment.Suitable treatment process is described in, for example, and among the WO 00/31090.Inorganic carrier (H) also can carry out chemical modification.For example, use NH
4SiF
6Handle silica gel and cause fluoridizing of silica gel surface; Equally, with nitrogenous-, contain the silica gel surface that fluoro-or sulfur-bearing-silane treatment silica gel also correspondingly provide modification.
The load of carrier (H) generally is to make it to contact with chromium cpd in solvent, removes down at 400～1100 ℃ and desolvates and calcined catalyst.Carrier (H) is suspended in the solvent or in the solution of chromium cpd.Chromium cpd generally is 0.001: 1～200: 1 with the ratio of the weight of carrier during the application, preferred 0.005: 1～100: 1.
According to embodiment preferred, the preparation method of chrome catalysts (A) adds a small amount of MgO and/or ZnO in inactive pre-catalyst, activate this mixture with traditional way then.This measure has improved the antistatic property of catalyzer.In order to activate, be at the dry pre-catalyst of 400～1100 ℃ temperature lower calcination catalyzer (A), for example, in fluidized-bed reactor, in oxygen containing oxidizing atmosphere.Preferably under inert atmosphere, cool off, in case adsorb oxygen.Also can as ammonium hexafluorosilicate, calcine under existing, use fluorine atom modified catalyst surface thus at fluorine cpd.Calcining in advance preferably occur in gas-phase fluidized-bed in.According to an embodiment preferred, earlier,, be subjected to pure inert gas simultaneously preferably to 250～350 ℃ with mixture heating up to 200～400 ℃, the rheomorphism of preferred nitrogen changes the rheomorphism of air into when mixture has been heated to the expectation terminal temperature.Make mixture keep 2～20h under terminal temperature, preferred 5～15h changes back rare gas element to air-flow then, and makes the mixture cooling.According to embodiment preferred, use in 600～800 ℃ of activatory supported chromium catalysts (A).
The catalyst system that especially preferably comprises at least a chrome catalysts (A), at least a iron catalyst (B), at least a carrier component (H) and preferred at least a activating compounds (J).
In a preferred embodiment of the invention, catalyst system comprises at least a activating compounds (J)., be that benchmark calculates preferably with their activatory catalyzer with excessive or use this activating compounds with stoichiometry.The mol ratio of catalyzer and activating compounds (J) generally can be 1: 0.1～1: 10000.The charged strong lewis acid of the general right and wrong of this activator compound, to contain the cationic ionic compound of Lewis acid or contain Bronsted acid be cationic ionic compound.Other details about the suitable activator of polymerizing catalyst of the present invention, especially about the preferred embodiment of non-charged strong lewis acid and the cationic definition of Lewis acid and this class activator, their preparation method and characteristic and the stoichiometry of using them, in the applicant's WO 05/103096, list in detail.Example is aikyiaiurnirsoxan beta, hydroxyai upsilonminoxanes, borine, boroxin, boric acid and two substituted boracic acids (borinic acids).Other example that is applicable to the non-charged strong lewis acid of making activating compounds provides drawing in this WO for reference 03/31090, WO 05/103096.
Both as an example also as highly preferred embodiment, being suitable for activating compounds (J) was following compound: aikyiaiurnirsoxan beta, non-charged strong lewis acid, to contain the cationic ionic compound of Lewis acid or contain Bronsted acid be cationic ionic compound.As for aikyiaiurnirsoxan beta, can use, for example, draw in the compound described in this WO for reference 00/31090.The aikyiaiurnirsoxan beta of particularly suitable is general formula (III) or open chain (IV) or ring-type aluminium alkoxide compound
R wherein
1B-R
4BRespectively be C independently of one another
1～C
6-alkyl, preferable methyl, ethyl, butyl or isobutyl-and I are 1～40, preferred 4～25 integer.
Useful especially aluminium alkoxide compound is methylaluminoxane (MAO).
The aikyiaiurnirsoxan beta that also can be used in the further modification that the some of them alkyl replaced by hydrogen atom or alkoxyl group, aryloxy, siloxy or amide group replaces formula (III) or the aluminium alkoxide compound (IV) as activating compounds (J).
Borine and boroxin are specially adapted to do activating compounds (J), as trialkylborane, triarylborane or trimethylboroxin.Preferred especially with the borine that brings to few two perfluorination aryl.More preferably with the compound that is selected from following inventory: triphenylborane, three (4-fluorophenyl) borine, three (3, the 5-difluorophenyl) borine, three (4-methyl fluoride phenyl) borine, three (pentafluorophenyl group) borine, three (tolyl) borine, three (3, the 5-3,5-dimethylphenyl) borine, three (3, the 5-difluorophenyl) borine or three (3,4, the 5-trifluorophenyl) borine.Very preferably activating compounds is three (pentafluorophenyl group) borine.Especially also to mention two substituted boracic acids that contain the perfluorination aryl, for example, (C
6H
5)
2BOH.The suitable Bor-base lewis acid compound that can be used as activating compounds (J) more generally defines drawing in this WO05/103096 for reference and provides, as previously discussed.
As draw as described in this WO for reference 9736937, containing negatively charged ion boron heterocyclic compound, as dimethylaniline base boron hydrogen benzene or trityl boron hydrogen benzene, also can be suitable for as activating compounds (J).Preferred ion activation compound (J) can contain the borate that brings to few two perfluorination aryl.Preferred especially four (pentafluorophenyl group) boric acid N, accelerine, four (pentafluorophenyl group) boric acid N especially, N-dimethyl hexamethylene ammonium, four (pentafluorophenyl group) boric acid N, N-dimethylbenzyl ammonium or four (pentafluorophenyl group) boric acid three benzene methyls.Two or more borate anions also may combine each other, as at dianion [(C
6F
6)
2B-C
6F
4-B (C
6F
5)
2]
2-In, or borate anion can be incorporated on the appropriate functional group of carrier surface by bridged bond.Other activating compounds (J) that is suitable for has been listed in and has drawn in this WO for reference 00/31090.
In addition, especially preferred activating compounds (J) preferably includes boron-aluminum compound, as two [two (pentafluorophenyl group boron oxygen base)] aluminium trimethide alkane (methylalane).The example of this class boron-aluminum compound be draw in this WO for reference 99/06414 disclosed those.Also can be with the mixture of all above-mentioned activating compounds (J).Preferred mixture comprises aikyiaiurnirsoxan beta, and especially methylaluminoxane and ionic compound especially contain ionic compound and/or non-charged strong lewis acid, especially three (pentafluorophenyl group) borine or the boroxins of four (pentafluorophenyl group) borate anion.
Catalyst system also can comprise the metallic compound as additional component (K), promptly as draw the metallic compound that defines with general expression, its use-pattern and stoichiometry and specific examples in this WO for reference 05/103096.Metallic compound also can be with random order and catalyzer (A) and (B), and randomly reacts with activating compounds (J) and carrier (H).
Unimportant on carrier (H), chrome catalysts (A), iron catalyst (B) and the combinable principle of temporal sequence of activating compounds (J).Behind processing step one by one, can as aliphatic hydrocarbon or aromatic hydrocarbons, clean each intermediate product with suitable inert solvent.Supported catalyst preferably obtains with free flowing powder.The example of industrial enforcement aforesaid method is described among WO 96/00243, WO 98/40419 or the WO 00/05277.Whether other fixing means is the pre-polymerized catalyst system, no matter place on the carrier earlier.Can make chrome catalysts (A) and iron catalyst (B) form with single catalyst system, for example, according to any preferred embodiment, randomly comprise the catalyst system of above-mentioned other component, contact with wanting polymeric alkene, or also they can be added reactor respectively.
It is every gram carrier (H) proportioning 1～200 μ mol that the preferred add-on of chrome catalysts (A) will make the interior chromium concn from chrome catalysts (A) of finished catalyst system, preferred 5～100 μ mol, especially preferred 10～70 μ mol.It is every gram carrier (H) proportioning 1～200 μ mol that the preferred add-on of iron catalyst (B) will make the interior concentration of iron from iron catalyst (B) of finished catalyst system, preferred 5～100 μ mol, especially preferred 10～70 μ mol.
For catalyst system, also can elder generation and alpha-olefin, preferably line style C
2～C
10-1-alkene, more preferably ethene or propylene carry out prepolymerization, then the prepolymerization catalyst solid of gained are used for actual polymerization.Catalyst solid used in the prepolymerization is preferably 1: 0.1 with the ratio that is aggregated to the monomeric quality on it～and 1: 1000, preferred 1: 1～1: 200.In addition, during the preparation of catalyst system or after, can add small amounts of olefins, preferred alpha-olefin is as vinyl cyclohexane, vinylbenzene or phenyl dimethyl vinyl silanes, as modified component; Antistatic or suitable inert compound is as wax or oil, as additive.The mol ratio of additive and chrome catalysts (A) and iron catalyst (B) sum normally 1: 1000～1000: 1, preferred 1: 5～20: 1.
The invention provides the method for the purposes of above-mentioned catalyst composition in vinyl polymerization and preparation multimodal polyethylene of the present invention, this method comprises the step that makes ethene and at least a alpha-olefin copolymer.
Therefore, the present invention also is provided at the catalyst system existence of the present invention method of olefin polymerization down.
Preferably in copolymerization process of the present invention, make ethene and the alpha-olefine polymerizing that preferably has 3～12 carbon atoms.Preferred alpha-olefin is the C of line style or branching
2～C
12-1-alkene, especially line style C
2～C
10-1-alkene, as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene, or the C of branching
2～C
10-1-alkene is as 4-methyl-1-pentene.Particularly preferred 1-alkene is C
4～C
20-1-alkene, especially line style C
6～C
10-1-alkene.Mixture that also can the various 1-alkene of polymerization.Preferred polymeric is at least a to be selected from following one group alpha-olefin: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene and 1-decene.The preferred use contains the monomer mixture of 50mol% ethene at least.
The polymerization of ethene of the present invention and alpha-olefin can be with industrial known polymerization preferably-60～350 ℃, more preferably 20～300 ℃, again more preferably under 25～150 ℃ the temperature and preferably at 0.5～4000bar, more preferably 1～100bar and most preferably carrying out under the pressure of 3～40bar.Polymerization can be in a known way in body, in suspensoid, in gas phase or in supercritical medium, in olefin polymerization reactor commonly used, carry out.Polymerization can be carried out with a step or multistep with interrupter method or preferred continuous processing.Method for high pressure polymerization in tubular reactor or autoclave, solution method, suspension method, stirring vapor phase process and gas fluidized bed method can.
Mean residence time is 0.5～5h preferably, more preferably 0.5～3h.As known in the art, carry out the more suitable pressure and temperature scope of polymerization and often depend on polymerization process.At 1000～4000bar, especially under the situation of the method for high pressure polymerization that carries out under 2000～3500bar pressure, also preferably set high polymerization temperature preferably.The preferred range of this class method for high pressure polymerization is 200～320 ℃, more preferably 220～290 ℃.Under the situation of low-pressure polymerization method, the softening temperature that preferably sets temperature ratio copolymer is low at least several times.In this class polymerization, especially preferably temperature is set in 50～180 ℃, preferred 70～120 ℃.Under the situation of suspension polymerization, preferred polymeric is carried out in suspension medium, and preferred unreactive hydrocarbons are as the mixture of Trimethylmethane or multiple hydrocarbon or carry out in monomer itself.Polymerization temperature is preferably-20～115 ℃, and pressure is generally 1～100bar.The intravital solids content that suspends is generally 10～80%.Polymerization can interrupter method, for example in stirring autoclave, or continuous processing, for example in tubular reactor, preferably in loop reactor, carry out.Especially preferably use the Phillips PF method described in US-A 3 242 150 and the US-A 3 248 179.Vapour phase polymerization is preferably at 30～125 ℃ with preferably carry out under 1～50bar pressure.
In above-mentioned various polymerizations, preferred especially gaseous polymerization is preferably carried out in gas-phase fluidized-bed reactor, and preferred solution polymerization and suspension polymerization preferably carry out in loop reactor and stirred tank.Vapour phase polymerization also can be condensed or super cohesion pattern is carried out, and makes the part recycle gas be cooled to loop back reactor below the dew point and as two-phase mixture therein.According to another alternate embodiment, also can allow polymkeric substance alternately pass through these two districts with the multi-region reactor that comprises two interconnected each other different polymeric areas with predetermined times.These two districts preferably have different polymerizing conditions, thereby carry out two different polymerization stages.This reactor is described in, for example, and among the WO 97/04015.If desired, similar and different polymerization stage also can be connected in series, to form the polymerization tandem in the reactor of two arranged in series.Also can adopt the parallel reactor of 2 kinds or multiple identical or different method to arrange.In addition, also can use molar mass regulator in the polymerization, as hydrogen, or typical additives, as static inhibitor.In order to obtain a high proportion of vinyl, preferably with a small amount of hydrogen or in the presence of no hydrogen, carry out polymerization.
Preferably in single reactor, especially in Gas-phase reactor, carry out polymerization.When using catalyst composition of the present invention, ethene can be made into multimodal polyethylene of the present invention with the polymerization that preferably has the alpha-olefin of 3～12 carbon atoms.Directly the polyethylene powders available from reactor demonstrates very high homogeneity, and is therefore different with the situation of series process, just needn't follow-uply extrude and can obtain uniform product.Preparation multimodal polyethylene of the present invention helps reducing energy consumption in reactor, does not need follow-up blend process and makes the molecular mass distribution of various polymkeric substance and the simple control of molecular mass fraction become possibility.In addition, also realized poly well blend.
Embodiment
The following example illustrates the present invention but does not limit its scope.
The percentage ratio of the single component of all that mention among the application is all based on weight, promptly based on the gross weight of correspondent composition that comprises these components or mixture, except as otherwise noted.
In this specification sheets and claim subsequently, used parameter is measured by the following method.
Density [g/cm
3] press ISO 1183 and measure.
Melt flow rate (MFR) MFR
21Press ISO1133 (190 ℃/21.6kg) measure down of 190 ℃ temperature and the load of 21.6kg.
Melt flow rate (MFR) MFR
5Press ISO1133 (190 ℃/5kg) measure down of 190 ℃ temperature and the load of 5kg.
Intrinsic viscosity is pressed EN ISO 1628-1 and is measured.
Weight-average molar mass M
w, mumber average molar mass M
nCarry out with the high-temperature gel permeation chromatography method with the mensuration of polymolecularity: use method (1995-02 version based on DIN 55672-1 derived from them, Februar 1995), on WATERS 150C, with following series connection pillar: 3 * SHODEXAT 806MS, 1 * SHODEX UT 807 and 1 * SHODEX AT-G, under following condition: solvent: 1,2,4-trichlorobenzene (having used 0.025wt%2,6-di-tert-butyl-4-methy phenol stabilization); Flow: 1ml/min, volume injected: 500 μ l, temperature: 135 ℃, proofread and correct with the PE standard model.Estimate with WIN-GPC.
Contents of ethylene is pressed ASTM D 6248-98 and is measured with the IR method.
Side chain number/1000 carbon atom is used
13C-NMR measures, as James.C.Randall, and JMS-REV.Macromol.Chem.Phys., C29 (2﹠amp; 3), 201-317 (1989) is described, and to comprise the CH of end group
3Total content/1000 carbon atom is that benchmark calculates.Do not comprise end group greater than CH
3Side chain, especially ethyl, butyl and hexyl side side chain number/1000 carbon atoms also measure with this method.
Holtrup method (W.Holtrup, Makromol.Chem.178,2335 (1977)) combination of the degree of branching in each polymer fractions
13C-NMR, as James.C.Randall, JMS-REV.Macromol.Chem.Phys., C29 (2﹠amp; 3), 201-317 (1989) is described, measures.
The content of comonomer side chain/1000 carbon atom with the FTIR 2000 of Perkin Elmer with infrared spectroscopic determination, and to comprise the CH of end group
3Base total content/1000 carbon atoms are that benchmark calculates.Co-monomer content is determined with multivariate data analysis.
Heptane and toluene are dry on molecular sieve.
Embodiment 1
The preparation of supported chromium catalysts
With 150g load chromium (0.3wt% is on carrier).Used carrier is that surface-area (BET) is 300m
2/ g and pore volume are the spraying drying SiO of 1.60ml/g
2Carrier.This kind carrier can be commercial available from Grace, and commodity are called XPO2170.In the such carrier of 135kg, add 192lCr (NO
3)
39H
2The solution (17g/l) of O in methyl alcohol, after the 1h, (900～300mbar) distillation method are removed and are desolvated with the decompression under 70～75 ℃.The intermediate product that obtains contains 0.3wt% chromium.
The carrier that 100g so handled is put into quartzy activator, this activator under nitrogen stream (130l/h) in 5h internal heating to 550 ℃.At 300 ℃, gas automatically is changed to airflow (130l/h) from the nitrogen circulation.Make temperature keep 2h at 550 ℃.Quartzy activator is cooled down, wherein automatically be converted to nitrogen stream from airflow at 300 ℃ of gases.Obtain the 62g chrome catalysts.
Embodiment 2
The prepolymerization of the chrome catalysts of embodiment 1
Chrome catalysts made among the 37g embodiment 1 is suspended in the 650ml heptane in the 1L four neck flasks, and flask disposes contact thermometer, Teflon blade agitator, inlet pipe, condenser and heating jacket.Heat this suspensoid to 63 ℃ and feeding ethene 60min (8l/h) under this temperature.Color is from rice brown (Cr
VI) become olive-green (Cr
II-III).With the stifling undissolved ethene of argon gas.Suspensoid is transferred on the glaze of glass filter and with the 500ml washed with heptane it.Make product under 0mbar, be dried to constant weight.Polymkeric substance accounts for the 24wt% of gross product.
Embodiment 3
2,6-two [1-(2-chloro-4,6-3,5-dimethylphenyl imino-) ethyl] the muriatic preparation of pyridine iron (II)
With 35.0g 2,6-diacetyl pyridine (0.215mol), 50g
(phosphorus oxide (V), phosphoric anhydride) and 76.8g (0.493mol) 2-chloro-4, the 6-xylidine is dissolved among the 1500ml THF.Under refluxad heat this mixture 42h.Output reaches 71.2% (GC/MS).At room temperature filter this mixture then.Clean filter cake with 50ml THF.Boil off the solvent in the combined filtrates.Add 250ml methyl alcohol and stir this mixture 1h.Form the yellow suspension body and isolate product with filtration method.(2 * 20ml) clean filter cakes drying then with methyl alcohol.Isolate the 58g part.This part is dissolved among the THF.Add FeCl
2* 4H
2O also at room temperature stirs the about 4h of this mixture.Form blue precipitation.Filter (room temperature) this blueness suspensoid, isolate complex compound.Clean filter cake (product) with pentane, then drying.Isolate the 46g complex compound.
Embodiment 4
Pre-polymerization chrome catalysts with the iron catalyst doping embodiment 2 of embodiment 3
The prepolymerization catalyst of 14.6g embodiment 2 is put into 250ml four neck flasks and dripped 2 of 0.1487g embodiment 3,6-two [(2-chloro-4,6-3,5-dimethylphenyl imino-) ethyl] (30wt% is in toluene for pyridine iron (II) muriate and 26.1mmol MAO, 4.75M, Albermale) suspensoid in 8ml toluene, and stir this mixture 2h.Obtain the ivory white powder of 20.3g.
Embodiment 5
Be used for polymeric solution
IPRA-solution
(70wt% Crompton) and with heptane is added to 100ml to get the solution of 8.5ml IPRA in hexane.
Get 0.55ml
AS 100-solution (available from Costenoble) also is added to 100ml with heptane.
Embodiment 6
Polymerization
At room temperature, with 1ml
AS 100-solution and 3ml IPRA-solution are put into the 1L autoclave, dash with argon gas and sweep and be heated to 70 ℃.With ethene the 400ml Trimethylmethane is compressed into autoclave and made pressure be raised to 40bar with ethene from sampling receptacle then.Add catalyzer made among the 82mg embodiment 4 with the spray gun spray.Start and measure and Controlling System, boost to 40bar automatically and keep this constant pressure with hexene and ethene.Evaporate hexene and constantly add ethene.Be aggregated under 70 ℃ and the 40bar and carry out 1h.The performance of processing condition and resulting polymers is listed in table 1 and 2, and wherein the performance of first polymer fractions is as follows: density is 0.970g/cm
3, no hexene is sneaked into, weight-average molar mass M
wBe 51000g/mol, polymolecularity M
w/ M
nBe 6.8, CH
3Sum/1000C is 4.6, and vinyl quantity/1000C is 2.38.
Embodiment 7
Polymerization
At room temperature, the 80g polyethylene specimen is put into 1L autoclave and be heated to 70 ℃.Be injected into 3ml IPRA solution and 1ml at 70 ℃ then
AS 100-solution.Under inert conditions, add the catalyzer made among the embodiment 4 of 197mg and make pressure be raised to 10bar with argon gas.Start and measure and Controlling System, boost to 20bar automatically and keep this constant pressure with ethene.Be aggregated under 70 ℃ and the 20bar and carry out 1h.The performance of processing condition and resulting polymers is listed in table 1 and 2.
Embodiment 8
Polymerization
At room temperature, put the 100g polyethylene specimen into the 1L autoclave, dash with argon gas and sweep, be heated to 70 ℃ then.Under 70 ℃, be injected into 4mlIPRA solution and 1ml then
AS 100-solution.Under inert conditions, add the catalyzer made among the 209mg embodiment 4 and make pressure be raised to 10bar with argon gas.Start and measure and Controlling System, boost to 20bar automatically and keep this constant pressure with hexene and ethene.Be aggregated under 70 ℃ and the 20bar and carry out 1h.The performance of processing condition and resulting polymers is listed in table 1 and 2.
Table 1
| Embodiment | Cat measures [mg] | Ethene amount [l] | C6 measures [ml] | Time [min] | Output [g] | Prod. [g/g] | [η] [dl/g] |
| Embodiment 6 | ?82 | 5.7 | 10 | ?60 | 30 | 366 | 10.84 |
| Embodiment 7 | ?197 | 79 | - | ?60 | 88 | 447 | 3.05 |
| Embodiment 8 | ?209 | 94 | 12 | ?60 | 101 | 483 | 2.40 |
Table 2
| Embodiment | M w [g/mol] | M n [g/mol] | M w/M n | Density [g/cm 3] | tot CH 3 [1/100 0C] | The two keys [1/100 0C] of trans | Vinyl double bond [1/100 0C] | C6 [％] |
| Embodiment 6 | 737795 | 6348 | 116 | 0.960 | 3.0 | 003 | 2.17 | 0.8 |
| Embodiment 7 | 234550 | 7205 | 32 | 0.967 | 3.5 | 0.02 | 2.28 | - |
| Embodiment 8 | 148260 | 5899 | 25 | 0.965 | 4.0 | 005 | 2.52 | 0.8 |
The more than abbreviation in the table:
The Cat catalyzer
Prod. restrain the catalyst production that numerical table shows with what used every gram catalyzer per hour obtained with polymkeric substance
[η] intrinsic viscosity
M
wWeight-average molar mass
M
nMumber average molar mass
M
w/ M
nThe ratio of heterogeneity index=weight-average molar mass and mumber average molar mass
Density polymers density
Tot CH
3/ 1000C is CH
3Total content/1000 carbon atom (comprising end group)
The two keys of trans are trans double bond number/1000 carbon atoms, press ASTM D 6248-98 and measure with the IR method
Vinyl double bond is contents of ethylene/1000 carbon atom, presses ASTM D 6248-98 and measures with the IR method
C6 is the content of hexene co-monomer.
Claims (9)
1. comprise at least a first ethene polymers fraction and at least a multimodal polyethylene that comprises the second ethene polymers fraction of the ethylene copolymer with second molecular weight that is higher than described first molecular weight that comprises the homopolymer with first molecular weight, the density of described multimodal polyethylene is 0.915～0.970g/cm
3, weight-average molar mass M
wBe 100000～900000g/mol and polymolecularity M
w/ M
nBe at least 15, wherein, the density of described at least a homopolymer is 0.950～0.975g/cm
3, weight-average molar mass M
wBe 10000～90000g/mol and polymolecularity M
w/ M
nGreater than 3 and less than 10, and the polymolecularity M of wherein said at least a multipolymer
w/ M
nBe 8～80.
2. according to the multimodal polyethylene of claim 1, the polymolecularity M of wherein said at least a ethylene copolymer
w/ M
nBe 8～80.
3. according to any one multimodal polyethylene in claim 1 or 2, comprise at least 1.5 vinyl/1000 carbon atom.
4. catalyst composition, it comprises:
(A) at least a based on chromic oxide chrome catalysts and
(B) iron catalyst of at least a formula (I),
Wherein the meaning of each symbol is as follows:
F and G are independently from each other:
Wherein
R
A, R
BRepresent hydrogen, C independently of one another
1～C
20-alkyl, C
2～C
20-thiazolinyl, C
6～C
20Have the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl, or SiR
11A 3, organic group R wherein
A, R
BAlso can be replaced by halogen, and/or in all cases, two radicals R
A, R
BAlso can be bonded to 5-or 6-unit ring each other,
R
C, R
DRepresent hydrogen, C independently of one another
1～C
20-alkyl, C
2～C
20-thiazolinyl, C
6～C
20Have the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl, or SiR
11A 3, organic group R wherein
C, R
DAlso can be replaced by halogen, and/or in all cases, two radicals R
C, R
DAlso can be bonded to 5-or 6-unit ring each other,
R
11ARepresent hydrogen, C independently of one another
1～C
22-alkyl, C
2～C
22-thiazolinyl, C
6～C
22Have the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl, and/or two radicals R
11AAlso can be bonded to 5-or 6-unit ring each other,
R
3-R
5Represent hydrogen, C independently of one another
1～C
22-alkyl, C
2～C
22-thiazolinyl, C
6～C
22Have the aralkyl, the NR that have 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl
16 2, OR
16, halogen, SiR
17 3, or comprise at least one 5-, 6-or 7-unit heterocyclic radical from the atom of N, P, O or S, wherein
Organic group R
3-R
5Also can be by halogen, NR
16 2, OR
16Or SiR
17 3Replace, and/or in all cases, two radicals R
3-R
5Can be bonded to 5-, 6-or 7-unit ring and/or in all cases, two radicals R each other
3-R
5Be bonded to 5-, 6-or 7-unit heterocyclic radical each other, described heterocyclic radical comprises at least one atom from N, P, O or S,
R
16Represent hydrogen, C independently of one another
1～C
22-alkyl, C
2～C
22-thiazolinyl, C
6～C
22Have the aralkyl or the SiR that have 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl
17 3, organic group R wherein
16Also can be replaced by halogen, and in all cases, two radicals R
16Also can be bonded to 5-or 6-unit ring,
R
17Represent hydrogen, C independently of one another
1～C
22-alkyl, C
2～C
22-thiazolinyl, C
6～C
22Have the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl or the alkyl, and in all cases, two radicals R
17Also can be bonded to 5-or 6-unit ring,
E
1-E
3Represent carbon, nitrogen or phosphorus independently of one another, especially carbon and
U E
1-E
3When being nitrogen and phosphorus, be 0 independently of one another, E
1-E
3When being carbon, be 1,
X represents fluorine, chlorine, bromine, iodine, hydrogen, C independently of one another
1～C
10-alkyl, C
2～C
10-thiazolinyl, C
6～C
20Have the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl, wherein organic group X also can be by R
18, NR
18 2, OR
18, SR
18, SO
3R
18, OC (O) R
18, CN, SCN, beta-diketon acid group, CO, BF
4 -, PF
6 -Or non-coordination macroanion replaces and radicals X wherein, as suitable, and bonding each other,
R
18Represent hydrogen, C independently of one another
1～C
20-alkyl, C
2～C
20-thiazolinyl, C
6～C
20Have the aralkyl or the SiR that have 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl, the alkyl
19 3, organic group R wherein
18Also can be by halogen or nitrogenous-and contain oxygen-Ji and replace, and in all cases, two radicals R
18Also can be bonded to 5-or 6-unit ring,
R
19Represent hydrogen, C independently of one another
1～C
20-alkyl, C
2～C
20-thiazolinyl, C
6～C
20Has the aralkyl that has 6～20 carbon atoms in 1～10 carbon atom and the aryl in-aryl or the alkyl, wherein organic group R
19Also can be by halogen or nitrogenous-and contain oxygen-Ji and replace, and in all cases, two radicals R
19Also can be bonded to 5-or 6-unit ring,
S is 1,2,3 or 4, especially 2 or 3,
D be neutral give body and
T is 0～4, especially 0,1 or 2.
5. according to the catalyst composition of claim 4, also comprise:
(H) at least a organic or inorganic carrier
(J) randomly, at least a activating compounds, and/or
(K) randomly, at least a metallic compound of the periodic table of elements the 1st, 2 or 13 family's metals.
6. according to the catalyst composition of one of claim 4 or 5, described catalyst composition is by following prepolymerization: with mass ratio be 1: 0.1～1: 200 with line style C
2～C
10-1 alkene is aggregated on the described catalyst composition.
7. according to the catalyst composition of one of claim 4 or 5 purposes in the copolymerization of the polymerization of alkene and/or alkene and at least a alpha-olefin.
8. according to the purposes of multimodal polyethylene in injection moulding, blowing and extrusion molding of one of claim 1～3.
9. preparation is according to the method for the multimodal polyethylene of any one in the claim 1～3, and therein ethylene and at least a alpha-olefin carry out copolymerization in the presence of the catalyst composition according to one of claim 4～6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07008743 | 2007-04-30 | ||
| EP07008743.2 | 2007-04-30 | ||
| PCT/EP2008/054654 WO2008132059A1 (en) | 2007-04-30 | 2008-04-17 | Polyethylene, process and catalyst composition for the preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102015784A true CN102015784A (en) | 2011-04-13 |
Family
ID=39639593
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008800230059A Pending CN102015784A (en) | 2007-04-30 | 2008-04-17 | Polyethylene, process and catalyst composition for the preparation thereof |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2142576A1 (en) |
| CN (1) | CN102015784A (en) |
| TW (1) | TW200904831A (en) |
| WO (1) | WO2008132059A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103534075A (en) * | 2011-05-10 | 2014-01-22 | 巴塞尔聚烯烃股份有限公司 | A process for homogenizing and pelletizing a polyethylene composition |
| CN111592606A (en) * | 2020-06-30 | 2020-08-28 | 中国石油化工科技开发有限公司 | Polyethylene powder and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102165005B (en) * | 2008-09-25 | 2014-09-10 | 巴塞尔聚烯烃股份有限公司 | Impact resistant LLDPE composition and films made thereof |
| US8846188B2 (en) | 2008-09-25 | 2014-09-30 | Basell Poliolefine GmbH | Impact resistant LLDPE composition and films made thereof |
| EP2196480A1 (en) * | 2008-12-15 | 2010-06-16 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Supported catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2001228639A1 (en) * | 2000-02-10 | 2001-08-20 | Bp Chemicals Limited | Polymerisation catalyst |
| WO2002102859A2 (en) * | 2001-04-30 | 2002-12-27 | W. R. Grace & Co.-Conn. | Coordination catalyst systems employing chromium support-agglomerate and method of their preparation |
| DE102005019393A1 (en) * | 2005-04-25 | 2006-10-26 | Basell Polyolefine Gmbh | Molding material, useful for the preparation of injection-molded body and screw valve, comprises ethylene monomer |
-
2008
- 2008-03-31 TW TW97111762A patent/TW200904831A/en unknown
- 2008-04-17 CN CN2008800230059A patent/CN102015784A/en active Pending
- 2008-04-17 WO PCT/EP2008/054654 patent/WO2008132059A1/en active Application Filing
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103534075A (en) * | 2011-05-10 | 2014-01-22 | 巴塞尔聚烯烃股份有限公司 | A process for homogenizing and pelletizing a polyethylene composition |
| US9289935B2 (en) | 2011-05-10 | 2016-03-22 | Basell Polyolefine Gmbh | Process for homogenizing and pelletizing a polyethylene composition |
| CN111592606A (en) * | 2020-06-30 | 2020-08-28 | 中国石油化工科技开发有限公司 | Polyethylene powder and preparation method thereof |
| CN111592606B (en) * | 2020-06-30 | 2023-05-02 | 中国石油化工科技开发有限公司 | Polyethylene powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
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| TW200904831A (en) | 2009-02-01 |
| WO2008132059A1 (en) | 2008-11-06 |
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